Two-dimensional large-area growth method for chalcogen compound, method for manufacturing cmos-type structure, film of chalcogen compound, electronic device comprising film of chalcogen compound, and cmos-type structure

ABSTRACT

Provided is a two-dimensional large-area growth method for a chalcogen compound, the method including: depositing a film of a transition metal element or a Group V element on a substrate; thereafter, uniformly diffusing a vaporized chalcogen element, a vaporized chalcogen precursor compound or a chalcogen compound represented by M′X′ 2+δ  within the film; and, thereafter, forming a film of a chalcogen compound represented by MX 2  by forming the chalcogen compound represented by MX 2  through post-heating.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of the U.S. patentapplication Ser. No. 14/778,863, filed on Sep. 21, 2015 which is aNational Stage application of International Application No.PCT/KR2014/002315, filed on Mar. 19, 2014, which claims priority fromKorean Patent Application No. 10-2013-0030687, filed on Mar. 22, 2013,the contents of all of which are incorporated herein by reference intheir entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a two-dimensional large-area growthmethod for a chalcogen compound, a method of manufacturing a CMOS-typestructure, a film of a chalcogen compound represented by MX₂ (wherein Mis a transition metal element or a Group V element and X is a chalcogenelement), an electronic device including a film of a chalcogen compoundrepresented by MX₂ and a CMOS-type structure.

This research was supported in part by the National Research Foundationof Korea (NRF-2013M3C1A3059590, NRF-2014M3A9D7070732).

This research was supported by Basic Science Research Program throughthe National Research Foundation of Korea (NRF) funded by the Ministryof Science, ICT & Future Planning (No. 2015R1A5A1037548).

This research was supported by the Commercializations Promotion Agencyfor R&D Outcomes (COMPA) funded by the Ministry of Science, ICT andFuture Planning (MISP).

2. Description of the Related Art

Chalcogen compounds such as transition metal chalcogen compounds form acommon crystalline structure, have electrically, magnetically andoptically large anisotropy, and exhibit a variety of unusual properties.Understanding for properties of such chalcogen compounds and applicationthereof have been interested.

There is a need to grow a two-dimensional plate-type chalcogen compoundhaving semiconductor-like properties on a large-area substrate bygrowing such chalcogen compounds to a large area. However, there islimitation of low mobility when a solution process is performed using aknown method, and there are a problem of slow growth and limitation inobtaining a uniform film upon application of chemical vapor depositionmethod wherein a chalcogen compound is deposited through chemical vapordeposition of a precursor compound.

SUMMARY OF THE INVENTION

Therefore, the present invention has been made in view of the aboveproblems, and it is an object of the present invention to provide atwo-dimensional large-area growth method for a chalcogen compoundexhibiting a high growth speed.

It is another object of the present invention to provide a method ofmanufacturing a CMOS-type structure, the method applying thetwo-dimensional large-area growth method for a chalcogen compound.

It is another object of the present invention to provide a uniformchalcogen compound film having high flexibility and mobility.

It is another object of the present invention to provide an electronicdevice including the chalcogen compound film.

It is a further object of the present invention to provide a CMOS-typestructure manufactured according to the method of manufacturing theCMOS-type structure.

In accordance with an aspect of the present invention, the above andother objects can be accomplished by the provision of a two-dimensionallarge-area growth method for a chalcogen compound, the methodcomprising:

forming a film of a transition metal element or a Group V element bydepositing the transition metal element or the Group V element on asubstrate;

diffusing the chalcogen element, the chalcogen precursor compound or thechalcogen compound represented by M′X′_(2+δ) into the film of thetransition metal element or the Group V element by contacting throughvaporization at least one selected from the group consisting ofchalcogen element, a chalcogen precursor compound and a chalcogencompound represented by M′X′_(2+δ) and combinations thereof with thefilm of the transition metal element or the Group V element, wherein M′is a transition metal element or a Group V element, X′ is a chalcogenelement, and 0≦δ≦0.5; and

forming a film of the chalcogen compound represented by MX₂ bypost-heating the film of the transition metal element or the Group Velement including the resultant diffused chalcogen element, chalcogenprecursor compound or chalcogen compound represented by M′X′_(2+δ),wherein M is a transition metal element or a Group V element and X is achalcogen element.

The transition metal may be at least one selected from the groupincluding Cr, Mo, W, Sn and combinations thereof, and the Group Velement may be at least one selected from the group including As, Sb, Biand combinations thereof.

The each chalcogen element may be at least one selected from the groupincluding S, Se, Te and combinations thereof, and the chalcogenprecursor compound is at least one selected from the group includingSO₂, H₂S, H₂Se, SeO₂, SeF₄, TeO₃, TeO₂, TeF₄ and combinations thereof.

The film of the transition metal element or the Group V element isdeposited to a thickness of about 1 nm to about 50 μm on the substrate.

The film of the transition metal element or the Group V element may bedeposited and formed through a physical or chemical vapor-phasesynthesis method.

The vaporized chalcogen element, chalcogen precursor compound, orchalcogen compound represented by M′X′_(2+δ) vaporized into the film ofthe transition metal element or the Group V element through a physicalor chemical vapor-phase synthesis method may be diffused using at leastone raw material selected from the chalcogen element, the chalcogenprecursor or the chalcogen compound represented by M′X′_(2+δ) andcombinations thereof.

The chalcogen element, the chalcogen precursor compound or the chalcogencompound represented by M′X′_(2+δ) may be diffused into the film of thetransition metal element or the Group V element at about 100 to about1500° C. by contacting through vaporization the chalcogen element, thechalcogen precursor compound or the chalcogen compound represented byM′X′_(2+δ) with the film of the transition metal element or the Group Velement.

The chalcogen element, the chalcogen precursor compound or the chalcogencompound represented by M′X′_(2+δ) vaporized into the film of thetransition metal element or the Group V element may be diffused througha method selected from the group consisting of chemical vapor deposition(CVD), thermal CVD, plasma enhanced chemical vapor deposition (PECVD),low pressure chemical vapor deposition (LPCVD), atomic layer deposition(ALD), pulsed laser deposition (PLD), sputtering and combinationsthereof, using at least one raw material selected from the chalcogenelement, the chalcogen precursor or the chalcogen compound representedby M′X′_(2+δ) and combinations thereof.

The vaporized chalcogen element, chalcogen precursor compound orchalcogen compound represented by M′X′_(2+δ) may be migrated by acarrier gas and diffused into the film of the transition metal elementor the Group V element.

The carrier gas may include at least one selected from the groupincluding iodine, bromine and combinations thereof.

The raw material may further include a carrier gas.

In the film of the transition metal element or the Group V elementcomprising the diffused chalcogen element, precursor compound orchalcogen compound represented by M′X′_(2+δ), an atom ratio of thechalcogen element to the transition metal element or the Group V elementmay be greater than 2.

Upon the post-heating, a large amount of the chalcogen element and aremainder of the precursor compound may be vaporized.

Upon the post-heating, the carrier gas may be vaporized.

The film of the chalcogen compound represented by MX₂ formed through thepost-heating may be a single-crystalline film or a poly-crystallinefilm.

The post-heating may be carried out at about 100 to about 1500° C.

The substrate may include at least one selected from the group includinga glass substrate, a Si substrate, a quartz substrate, a sapphiresubstrate and combinations thereof.

The substrate may be a rigid substrate or a flexible substrate.

The two-dimensional large-area growth method for the chalcogen compoundmay further comprise recrystallizing the chalcogen compound representedby MX₂ by annealing the film of the chalcogen compound represented byMX₂.

The recrystallizing may be carried out through energy beam irradiation.

In accordance with another aspect of the present invention, there isprovided a method of manufacturing a CMOS-type structure, the methodcomprising:

forming a patterned film of a first transition metal element or a firstGroup V element on a substrate by patterning and depositing a firstn-type transition metal element or the first Group V element on thesubstrate;

forming a patterned film of a second transition metal element or asecond Group V element on a substrate by pattering and depositing asecond p-type transition metal element or the second Group V element onthe substrate;

diffusing the chalcogen element, the chalcogen precursor compound or thechalcogen compound represented by M′X′_(2+δ) into the patterned film ofthe first transition metal element or the first Group V element and thepatterned film of the second transition metal element or the secondGroup V element by contacting through vaporization at least one selectedfrom the group consisting of a chalcogen element, a chalcogen precursorcompound and a chalcogen compound represented by M′X′_(2+δ) andcombinations thereof with the patterned film of the first transitionmetal element or the first Group V element and the patterned film of thesecond transition metal element or the second Group V element, whereinM′ is a transition metal element or a Group V element, X′ is a chalcogenelement, and 0≦δ≦0.5; and

obtaining a complementary metal oxide semiconductor (CMOS)-typestructure comprising an N channel (such as MoS₂, MoSe₂, MoTe₂ etc.)metal oxide semiconductor (NMOS) and a P channel (such as WS₂, WSe₂,WTe₂ etc.) metal oxide semiconductor (PMOS) by forming a chalcogencompound represented by MX₂ through post-heating of the patterned filmcomprising the diffused chalcogen element chalcogen precursor compoundor chalcogen compound represented by M′X′_(2+δ) and thus by forming apatterned film of the chalcogen compound represented by MX₂, wherein Mis a transition metal element or a Group V element and X is a chalcogenelement.

The vaporized chalcogen element, chalcogen precursor compound, orchalcogen compound represented by M′X′_(2+δ) vaporized into thepatterned film through a physical or chemical vapor-phase synthesismethod may be diffused using at least one raw material selected from thechalcogen element, the chalcogen precursor or the chalcogen compoundrepresented by M′X′_(2+δ) and combinations thereof.

The chalcogen element, the chalcogen precursor compound or the chalcogencompound represented by M′X′_(2+δ) vaporized into the patterned film maybe diffused through a method selected from the group consisting ofchemical vapor deposition (CVD), thermal CVD, plasma enhanced chemicalvapor deposition (PECVD), low pressure chemical vapor deposition(LPCVD), atomic layer deposition (ALD), pulsed laser deposition (PLD),sputtering and combinations thereof, using at least one raw materialselected from the chalcogen element, the chalcogen precursor or thechalcogen compound represented by M′X′_(2+δ) and combinations thereof.

The vaporized chalcogen element, chalcogen precursor compound orchalcogen compound represented by M′X′_(2+δ) diffused into the patternedfilms may be migrated by a carrier gas and diffused into the film.

The raw material may further include a carrier gas.

The carrier gas may include at least one selected from the groupcomprising iodine (I), bromine (Br) and combinations thereof.

In the patterned film including the diffused chalcogen element,precursor compound or chalcogen compound represented by M′X′_(2+δ), anatom ratio of the chalcogen element to a total of the transition metalelement or the Group V element may be greater than 2.

The substrate may be at least one selected from the group including aglass substrate, a Si substrate, a quartz substrate, a sapphiresubstrate and combinations thereof.

The substrate may be a rigid substrate or a flexible substrate.

The method of manufacturing a CMOS-type structure may further includerecrystallizing the chalcogen compound represented by MX₂ by annealingthe CMOS-type structure obtained through the post-heating.

In accordance with another aspect of the present invention, there isprovided a film of a chalcogen compound represented by MX₂ preparedthrough the two-dimensional large-area growth method, wherein M is atransition metal element or a Group V element and X is a chalcogenelement.

The chalcogen compound represented by MX₂ may include at least oneselected from the group consisting of MoS₂, MoSe₂, WSe₂, MoTe₂, SnSe₂and combinations thereof.

The film of the chalcogen compound represented by MX₂ may be acrystalline film having a single-layer structure or a multi-layerstructure.

The film of the chalcogen compound represented by MX₂ may be asingle-crystalline film or a poly-crystalline film.

In accordance with another aspect of the present invention, there isprovided an electronic device comprising a film of a chalcogen compoundrepresented by MX₂ prepared through the two-dimensional large-areagrowth method, wherein M is a transition metal element or a Group Velement and X is a chalcogen element.

The electronic device may be a transistor or a diode.

The electronic device may be a transistor comprising a plurality ofelectrodes comprising a gate, a drain and a source, and a semiconductorchannel formed between the drain and the source electrode due to thefilm of the chalcogen compound represented by MX₂.

In accordance with a further aspect of the present invention, there isprovided a CMOS-type structure manufactured according to the method ofmanufacturing a CMOS-type structure.

The CMOS-type structure may be used in an invertor, a logic element, amemory, a display, a backplane, RF, AC or DC.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other objects, features and other advantages of thepresent invention will be more clearly understood from the followingdetailed description taken in conjunction with the accompanyingdrawings, in which:

FIG. 1 is a plan view illustrating a CMOS-type structure manufactured bya method of manufacturing a CMOS-type structure according to anembodiment of the present invention;

FIG. 2 is a schematic view illustrating a multi-layer chalcogen compoundstructure represented by MX₂, where M is a transition metal element or aGroup V element and X is a chalcogen element;

FIG. 3 is a graph illustrating MoSe₂ measurement results for films ofchalcogen compounds represented by MX₂, where M is a transition metalelement or a Group V element and X is a chalcogen element, preparedaccording to Examples 1 and 2, and films according to ComparativeExamples 1 to 4;

FIG. 4 is a graph illustrating MoSe₂ measurement results for films ofchalcogen compounds represented by MX₂ prepared according to Examples 1and 2, where M is a transition metal element or a Group V element and Xis a chalcogen element, and films according to Comparative Examples 1 to4;

FIG. 5 is a view illustrating an excimer laser beam irradiated to achalcogen compound;

FIG. 6 is a view schematically illustrating that an amorphous materialis recrystallized into a poly-crystalline material through laser beamirradiation and thus a grain boundary is widened;

FIGS. 7, 8 and 9 are graphs illustrating characteristics before/afterlaser beam irradiation;

FIG. 10 is a view illustrating absorption spectra of MoS₂ crystals, thethicknesses of which are different;

FIG. 11 is a view illustrating a band structure of bulk MoS₂;

FIG. 12 is a view illustrating an E-k diagram of a direct transitionband gap;

FIG. 13 is a view illustrating an E-k diagram of indirect transitionband gap;

FIG. 14 is a view illustrating Id-Vgs characteristic curves of a MoS₂phototransistor; and

FIG. 15 is a view illustrating three solids.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Exemplary embodiments will now be described more fully with reference tothe accompanying drawings to clarify aspects, features and advantages ofthe inventive concept. This invention may, however, be embodied in manydifferent forms and should not be construed as limited to the exemplaryembodiments set forth herein.

In an embodiment of the present invention, provided is a two-dimensionallarge-area growth method for a chalcogen compound, the methodcomprising: forming a film of a transition metal element or a Group Velement by depositing the transition metal element or the Group Velement on a substrate; diffusing the chalcogen element, the chalcogenprecursor compound or the chalcogen compound represented by M′X′_(2+δ)into the film of the transition metal element or the Group V element bycontacting through vaporization at least one selected from the groupconsisting of a chalcogen element, a chalcogen precursor compound and achalcogen compound represented by M′X′_(2+δ) and combinations thereofwith the film of the transition metal element or the Group V element;and forming a film of the chalcogen compound represented by MX₂ bypost-heating the film of the transition metal element or the Group Velement including the resultant diffused chalcogen element, chalcogenprecursor compound or chalcogen compound represented by M′X′_(2+δ),wherein M is a transition metal element or a Group V element and X is achalcogen element, wherein M′ is a transition metal element or a Group Velement, X′ is a chalcogen element, and 0≦δ≦0.5.

The chalcogen compound represented by MX₂ is a material formingtwo-dimensional nanoplate structure, and may be usefully applied as anext-generation semiconductor film material having high flexibility andmobility.

FIG. 2 illustrated a schematic view of a multi-layer crystal structureof the chalcogen compound represented by MX₂. As illustrated in FIG. 2,the chalcogen compound represented by MX₂ may form a single-layercrystal in which an M element and an X element are two-dimensionallycovalent-bonded. Such a single-layer is vertically stacked and thus amulti-layer crystal may be formed through van der Waals between layers.Upon formation of the multi-layer crystal, the thickness (d) betweenlayers in MoS₂ may be approximately 6.5 Å.

A film obtained according to the two-dimensional large-area growthmethod for a chalcogen compound may be a single-layer or multi-layerfilm formed from the chalcogen compound represented by MX₂.

A large-area film may be obtained by growing the chalcogen compoundrepresented by MX₂ into a large-area film according to thetwo-dimensional large-area growth method for a chalcogen compound. Sucha chalcogen compound film may be usefully used as a thin-filmsemiconductor material.

A film of the chalcogen compound represented by MX₂ obtained accordingto the two-dimensional large-area growth method for a chalcogen compoundis uniform and has high mobility and crystallinity. In addition, growthspeed thereof is high.

The chalcogen element and the chalcogen compound represented byM′X′_(2+δ) may be used as, for example, a raw material of a solid suchas a powder, and the chalcogen precursor compound may be used as a gas.

In particular, the transition metal may be at least one selected fromthe group including Cr, Mo, W, Sn and combinations thereof.

In particular, the Group V element may be at least one selected from thegroup including As, Sb, Bi and combinations thereof.

In particular, the each chalcogen element may be at least one selectedfrom the group including S, Se, Te and combinations thereof.

In particular, examples of the chalcogen precursor compound includesulfur-containing gases such as SO₂ and H₂S, selenium-containing gasessuch as H₂Se, SeO₂ and SeF₄, tellurium-containing gases such as TeO₃,TeO₂ and TeF₄, and combinations thereof.

In particular, the chalcogen compound represented by MX₂ and M′X′_(2+δ)may include at least one selected from the group consisting of MoS₂,WS₂, MoSe₂, WSe₂, MoTe₂, SnSe₂ and combinations thereof.

In regard to the two-dimensional large-area growth method for achalcogen compound, the film of the transition metal element or a GroupV element is first deposited on the substrate. Here, the film of thetransition metal element or the Group V element may have a thickness ofabout 1 nm to about 50 μm. The film of the transition metal element orthe Group V element is formed within this range and, thereafter, thevaporized chalcogen element, chalcogen precursor compound or thechalcogen compound represented by M′X′_(2+δ) may be uniformly diffusedwithin the film.

The film of the transition metal element or the Group V element may bedeposited through a publicly known method, e.g., a physical or chemicalvapor-phase synthesis method, without limitation. In particular, thefilm may be deposited through chemical vapor deposition (CVD), thermalCVD, plasma enhanced chemical vapor deposition (PECVD), low pressurechemical vapor deposition (LPCVD), atomic layer deposition (ALD), pulsedlaser deposition (PLD), sputtering, or the like.

Subsequently, the chalcogen element, chalcogen precursor compound orchalcogen compound represented by M′X′_(2+δ) is diffused into the filmof the transition metal element or the Group V element.

In an embodiment, at least one selected from the group consisting of thechalcogen element, the chalcogen precursor or the chalcogen compoundrepresented by M′X′_(2+δ) and combinations thereof as a raw material maybe diffused into the film of the transition metal element or the Group Velement through a physical or chemical vapor-phase synthesis methodusing.

In particular, the vaporized chalcogen element, chalcogen precursor orchalcogen compound represented by M′X′_(2+δ) may be diffused into thefilm of the transition metal element or the Group V element through amethod selected from the group consisting of chemical vapor deposition(CVD), thermal CVD, plasma enhanced chemical vapor deposition (PECVD),low pressure chemical vapor deposition (LPCVD), atomic layer deposition(ALD), pulsed laser deposition (PLD), sputtering and combinationsthereof.

Vaporization contacting the chalcogen element, the chalcogen precursoror the chalcogen compound represented by M′X′_(2+δ) with the film of thetransition metal element or the Group V element to diffuse the same intothe film of the transition metal element or the Group V element may becarried out at, for example, about 100° C. to about 1500° C.

The vaporized chalcogen element, chalcogen precursor or chalcogencompound represented by M′X′_(2+δ) diffused into the film of thetransition metal element or the Group V element is migrated by a carriergas and may be diffused into the film.

When the chemical vapor deposition method (CVD) and a modified chemicalvapor deposition method are used, a raw material of the chalcogenelement or chalcogen compound and a carrier gas may be mixed and used.

The carrier gas may include at least one selected from the groupincluding iodine (I), bromine (Br) and combinations thereof.

A raw material including at least one selected from the group consistingof the chalcogen element, the chalcogen precursor compound, thevaporized chalcogen compound represented by M′X′_(2+δ) and combinationsthereof may be used within a amount range within which an atom ratio ofthe chalcogen element to the resultant film of the transition metalelement or the Group V element including the diffused chalcogen elementor chalcogen compound is greater than 2.

When the film of the transition metal element or the Group V elementincluding the diffused chalcogen element, precursor compound orchalcogen compound represented by M′X′_(2+δ) is post-heated, a chalcogencompound represented by MX₂ is formed. Here, as described above, theatom ratio of the chalcogen element to the transition metal element orthe Group V element is greater than 2, and thus, remainders of largeamounts of the chalcogen element and chalcogen precursor compound isvaporized due to heat.

Upon the post-heating, the carrier gas is vaporized together.

The post-heating may be carried out about 100 to about 1500□.

Depending upon temperature generated through the post-heating,single-crystalline, poly-crystalline or noncrystalline chalcogencompound film may be formed.

In an embodiment, the film of the chalcogen compound represented by MX₂may form a crystalline film having a single-layer structure or amulti-layer structure.

In another embodiment, the film of the chalcogen compound represented byMX₂ formed through the post-heating may be a single-crystalline film ora poly-crystalline film.

The film of the chalcogen compound represented by MX₂ formed through thepost-heating may have a thickness of about 1 nm to about 50 μm.

A substrate on which the film of the transition metal element or theGroup V element is formed may include at least one selected from thegroup including glass, a substrate formed with an inorganic material(Si, quartz, sapphire, or the like) and combinations thereof.

In regard to the two-dimensional large-area growth method for achalcogen compound, the substrate may be a rigid substrate or a flexiblesubstrate without limitation.

As described above, a film prepared through the two-dimensionallarge-area growth method for a chalcogen compound may be formed into asingle-crystalline type, a poly-crystalline type or noncrystalline typedepending upon post-heating temperature. In order to increasecrystallinity of such a noncrystalline film or a film having amorphousand crystalline properties, annealing may be additionally carried out.

The two-dimensional large-area growth method for the chalcogen compoundmay further comprise recrystallizing the chalcogen compound representedby MX₂ by annealing the film of the chalcogen compound represented byMX₂.

In an embodiment, the recrystallizing may be carried out through energybeam irradiation.

With regard to the annealing, by performing energy beam irradiationinstead of heat treatment, damage of a substrate may be prevented whileincreasing mobility of a chalcogen compound. In particular, mobility ofa material may be enhanced by recrystallizing instantaneously anoncrystalline material to a single-crystalline or a poly-crystallinematerial through femtosecond laser annealing.

The laser annealing may facilitate crystallization of a chalcogencompound as a channel material and may decrease contact resistance byfunctioning in a bonding portion between a semiconductor and a conductorto enhance electrical conductivity.

As illustrated in FIG. 5, the laser annealing may be excimer laserannealing. In FIG. 5, a chalcogen compound that may be included as anamorphous material in a film is recrystallized to a single-crystallineor a poly-crystalline material by irradiating a laser beam 60 to a filmof a chalcogen compound formed on a substrate 40. The film of thechalcogen compound may be a film formed after the post-heating of thetwo-dimensional large-area growth method. As illustrated in FIG. 6, arecrystallized single-layer or multi-layer chalcogen compound isrecrystallized from noncrystalline 30 to poly-crystalline 20 and thus agrain boundary is extended. Accordingly, scattering is prevented andthus mobility is increased. In addition, bonding resistance of a bondingportion between a multi-layer chalcogen compound and a source/drainelectrode is enhanced through excimer laser annealing and thus mobilityis accelerated.

The recrystallizing described above may be carried out throughfemtosecond laser annealing, and a chalcogen compound is recrystallizedwithout mechanical damage for a substrate, thereby forming asemiconductor channel material.

FIGS. 7, 8 and 9 illustrates curves representing characteristics beforeor after irradiating a laser beam onto a noncrystalline chalcogencompound film.

As illustrated in FIG. 7, it can be known that drain current isdifferent before/after laser annealing and thus mobility is enhanced. Inaddition, FIG. 8 illustrates drain current before laser annealing, andFIG. 9 illustrates drain current after laser annealing. After laserannealing, a noncrystalline chalcogen compound is recrystallized to asingle-crystalline or multiple-crystalline chalcogen compound and thusdrain current is further increased.

In another embodiment of the present invention, provided is a method ofmanufacturing a CMOS-type structure, the method comprising: forming apatterned film of a first transition metal element or a first Group Velement on a substrate by patterning and depositing a first n-typetransition metal element or the first Group V element on the substrate;forming a patterned film of a second transition metal element or aSecond Group V element on a substrate by pattering and depositing asecond p-type transition metal element or the second Group V element onthe substrate; diffusing the chalcogen element, the chalcogen precursorcompound or the chalcogen compound represented by M′X′_(2+δ) into thepatterned film of the first transition metal element or the first GroupV element and the patterned film of the second transition metal elementor the second Group V element by contacting through vaporization atleast one selected from the group consisting of a chalcogen element, achalcogen precursor compound and a chalcogen compound represented byM′X′_(2+δ) and combinations thereof with the patterned film of the firsttransition metal element or the first Group V element and the patternedfilm of the second transition metal element or the second Group Velement; and obtaining a complementary metal oxide semiconductor(CMOS)-type structure comprising an N channel metal oxide semiconductor(NMOS) and a P channel metal oxide semiconductor (PMOS) by forming achalcogen compound represented by MX₂ through post-heating of thepatterned film comprising the diffused chalcogen element chalcogenprecursor compound or chalcogen compound represented by M′X′_(2+δ) andthus by forming a patterned film of the chalcogen compound representedby MX₂, wherein M is a transition metal element or a Group V element andX is a chalcogen element.

The method of manufacturing a CMOS-type structure is a method ofmanufacturing a CMOS-type structure from a chalcogen compound using thetwo-dimensional large-area growth method for a chalcogen compound.

FIG. 1 illustrates a plan view of an embodiment of a CMOS-type structuremanufactured according to the method of manufacturing a CMOS-typestructure.

As illustrated in FIG. 1, in order to realize CMOS including a patternedNMOS 1 and PMOS 2, each of an n-type first transition metal element orfirst Group V element according to a pattern of the NMOS 1 and a p-typesecond transition metal element or second Group V element according to apattern of the PMOS 2 is patterned on a substrate and thus patterneddeposition films are formed.

FIG. 1 illustrates pattern shapes of the NMOS 1 and the PMOS 2 as anembodiment. The pattern shape of each of the NMOS 1 and the PMOS 2 maybe different without limitation depending upon a desired CMOS-typestructure.

When, with a substrate on which a patterned deposition film of each ofthe n-type first transition metal element or first Group V element andthe p-type second transition metal element or second Group V element isformed, a chalcogen element or chalcogen compound is contacted throughvaporization using the two-dimensional large-area growth method for achalcogen compound, the chalcogen element, chalcogen precursor compoundor a chalcogen compound represented by M′X′_(2+δ) is diffused into apatterned films 1 and 2.

Detailed descriptions for the first or second transition metal elementand the first or second Group V element are the same as those for thetransition metal element and the Group V element described in thetwo-dimensional large-area growth method for a chalcogen compounddescribed above.

Detailed descriptions for a method of diffusing the chalcogen element orchalcogen compound are the same as those for the two-dimensionallarge-area growth method for a chalcogen compound described above. Thatis, at least one raw material selected from the chalcogen element, thechalcogen precursor or the chalcogen compound represented by M′X′_(2+δ)and combinations thereof may be diffused into the patterned films 1 and2 of the first or second transition metal element or the first or secondGroup V element through a physical or chemical vapor-phase synthesismethod.

In particular, the chalcogen element or the chalcogen compound is usedas a raw material, and the vaporized chalcogen element or the vaporizedchalcogen compound may be diffused into the patterned films 1 and 2through a method selected from the group consisting of chemical vapordeposition (CVD), thermal CVD, plasma enhanced chemical vapor deposition(PECVD), low pressure chemical vapor deposition (LPCVD), atomic layerdeposition (ALD), pulsed laser deposition (PLD), sputtering andcombinations thereof.

Detailed descriptions for the chalcogen element, the chalcogen precursoror the chalcogen compound represented by M′X′_(2+δ) diffused throughvaporization are the same as those for the two-dimensional large-areagrowth method for a chalcogen compound described above.

The vaporized chalcogen element, chalcogen precursor compound orchalcogen compound represented by M′X′_(2+δ) diffused into the patternedfilms 1 and 2 may be migrated by a carrier gas and diffused into thefilm. Accordingly, the raw material used in the physical or chemicalvapor-phase synthesis method may further include a carrier gas.

The carrier gas may include at least one selected from the groupcomprising iodine (I), bromine (Br) and combinations thereof.

In the patterned film including the diffused chalcogen element,chalcogen precursor compound or chalcogen compound represented byM′X′_(2+δ), an atom ratio of the chalcogen element to a total of thetransition metal element or the Group V element may be greater than 2.

Subsequently, when post-heating is performed, a chalcogen compoundrepresented by MX₂ is formed and, at the same time, each of the NMOS 1and the PMOS 2 is formed, whereby a CMOS-type structure 10 including theNMOS 1 and the PMOS 2 is manufactured.

Detailed descriptions for the chalcogen compound represented by MX₂formed after the post-heating are the same as those for thetwo-dimensional large-area growth method for a chalcogen compound.

Detailed descriptions for the post-heating are the same as those for thetwo-dimensional large-area growth method for a chalcogen compound.

In addition, the method of manufacturing a CMOS-type structure mayfurther include recrystallizing the chalcogen compound represented byMX₂ by annealing the CMOS-type structure obtained through thepost-heating.

The substrate 3 may be at least one selected from the group including aglass substrate, a Si substrate, a quartz substrate, a sapphiresubstrate and combinations thereof.

The substrate may be a rigid substrate or a flexible substrate.

In another embodiment of the present invention, provided is a film of achalcogen compound represented by MX₂, which is prepared according tothe two-dimensional large-area growth method for a chalcogen compound.In the chalcogen compound represented by MX₂, M is a transition metalelement or a Group V element and X is a chalcogen element.

As described above, the film of the chalcogen compound represented byMX₂ may be formed as a large area.

In particular, the film of the chalcogen compound represented by MX₂ maybe a film of at least one chalcogen compound selected from the groupconsisting of, MoS₂, MoSe₂, WSe₂, MoTe₂, SnSe₂ and combinations thereof.

The film of the chalcogen compound represented by MX₂ may be acrystalline film having a single-layer structure or a multi-layerstructure.

The chalcogen compound represented by MX₂ forming the single-layercrystalline film absorbs light through a direct transition band gap, andthe chalcogen compound represented by MX₂ forming the multi-layercrystalline film absorbs light through an indirect transition band gap.

The chalcogen compound represented by MX₂ forming the multi-layercrystalline film may absorbs wavelengths of from a UV area to anear-infrared ray area.

A single-layer MoS₂ structure and a transistor having single-layer MoS₂are the same as illustrated in FIGS. 1 and 2. As illustrated in FIG. 1,a single-layer MoS₂ crystal has a vertically staked structure and suchsingle layer has a thickness of 6.5 Å and is formed by van der Waalsinteraction.

Hereinafter, an embodiment of the chalcogen compound represented by MoS₂is described, and difference between a single-layer chalcogen compoundand a multi-layer chalcogen compound is described.

For example, MoS₂ as a single-layer chalcogen compound has a unique bandgap of 1.8 eV, and unique mobility of the material is 0.5 to 3cm²V⁻¹s⁻¹. The single-layer MoS₂ may absorb a wavelength of below about700 nm as illustrated as T2 and T3 graphs of FIG. 10. In FIG. 10, T1, T2and T3 denote the thickness of the MoS₂ crystal, and a thickness sizeorder is as follows: foT1>T2>T3. In particular, T1 is about 40 nm, T2 isabout 4 nm and T3 is about 1 nm.

In FIGS. 10 and 11, “A” and “B” as absorption peaks correspond to adirect transition band gap energy-separated from valance band spin-orbitbonding, a tail “I” corresponds to an indirect transition band gap.

Meanwhile, as illustrated in FIG. 12, a direct transition band gapoccurs when energy E_(v)(k) of a valence band is generated as the samewave number k as energy E_(c)(k) of a conduction band. As illustrated inFIG. 13, an event that two piece of energy is generated as differentwave numbers is called an indirect transition band gap. In the directtransition band gap, a valence electron is directly transited to aconduction band by light radiation energy hν, but, in the indirecttransition band gap, a valence electron is indirectly transited to aconduction band. In this case, phonon of energy E_(ph) occurs.

Accordingly, in the direct transition band gap, hν=E_(g), and, in theindirect transition band gap, hν=E_(g+)E_(ph). As such, E_(ph) isgenerated in the indirect transition band gap and thus an energy gap ina direct transition band gap is lowered from 1.8 eV (single-layer MoS₂)to 1.35 eV (multi-layer MoS₂). Here, in the case of single-layer MoS₂,MoS₂ having three layers or more is preferable.

When an energy gap is lowered from 1.8 eV to 1.35 eV, a wavelength valueis changed according to Mathematical Equation 1.

$\begin{matrix}{\lambda = \frac{1.24}{E_{g}}} & {{Mathematical}\mspace{14mu} {Equation}\mspace{14mu} 1}\end{matrix}$

Energy gaps of 1.8 eV and 1.35 seV are compared. When an energy gap is1.35 seV, i.e. a small band gap, a wavelength (λ) is increased.Comparing the case of using the single-layer MoS₂ and the case of usingthe multi-layer MoS₂, a broader wavelength may be absorbed when themulti-layer MoS₂ is used, as illustrated in T1, T2 and T3 graphs of FIG.10.

In the case of the single-layer MoS₂, a wavelength of below 700 nm maybe generally absorbed, but, in the multi-layer MoS₂ (preferably havingthree layers or more) according to the present invention, allwavelengths of below 1000 nm may be absorbed, which means that fromnear-infrared ray (near IR) to UV wavelengths may be detected.

In a single-layer or multi-layer chalcogen compound device, I_(d)difference between when light is not incident and when light is incident(633 nm, strength of 50 mWcm⁻²) is about 10₃, as illustrated in FIG. 14.Accordingly, the single-layer or multi-layer chalcogen compound devicemay be used as a switching device.

The film of the chalcogen compound represented by MX₂ may be asingle-crystalline film or a poly-crystalline film.

In general, solids used in semiconductor are classified into threetypes, i.e. single-crystalline, poly-crystalline and noncrystalline.Crystalline is defined as a regular molecular arrangement. Insingle-crystalline, such a regular arrangement is uniformly formed in anoverall solid. In poly-crystalline, a crystal is partially formed, butan overall one uniform crystal is formed. Meanwhile, noncrystalline is asolid, but, in noncrystalline, molecular are randomly arranged and thereis no regulation. Examples thereof are illustrated as asingle-crystalline 10, a poly-crystalline 20 and a noncrystalline 30 inFIG. 15.

Here, the single-crystalline is a material formed of one grain, and thepoly-crystalline is a material formed of a variety of grains thatrespectively have a different crystal direction. As illustrated in FIG.15, in the noncrystalline, molecules are randomly arranged andscattering is generated due to impurities, whereby electron migrationbecomes slow. Accordingly, when a semiconductor channel is formed usingnoncrystalline, mobility is poor.

Here, the single-layer or multi-layer chalcogen compound may be formedinto a large area through the two-dimensional large-area growth methodfor a chalcogen compound described above. In addition, as describedabove, a noncrystalline chalcogen compound may be included according toprocess temperature conditions. In this case, crystallinity is increasedby recrystallizing through an additional annealing process and thusunique mobility of the chalcogen compound may be realized.

As described above, the annealing increases mobility of a material byinstantaneously recrystallizing a noncrystalline material to asingle-crystalline or poly-crystalline material through, for example,femtosecond laser annealing. The laser annealing may facilitatecrystallization of a channel material and enhance electricallyconductivity by decreasing contact resistance through application to abonding portion between a semiconductor and conductor.

In another embodiment of the present invention, an electronic deviceincluding a film of the chalcogen compound represented by MX₂ preparedaccording to the two-dimensional large-area growth method for achalcogen compound is provided. In the chalcogen compound represented byMX₂, M is a transition metal element or a Group V element and the X is achalcogen element.

In particular, the electronic device may be a transistor, a diode, orthe like.

In an embodiment, the electronic device is a transistor comprising aplurality of electrodes comprising a gate, a drain and a source, and asemiconductor channel formed between the drain and the source electrodedue to the film of the chalcogen compound represented by MX₂. In theelectronic device, a channel material is formed using the film of achalcogen compound, and thus, TFT suitable for next-generation displaysmay be constituted. When a gate, a drain and a source electrode areapplied to a transparent electrode, a transparent display having hightransmittance may be realized.

In another embodiment of the present invention, a CMOS-type structuremanufactured according to the method of manufacturing a CMOS-typestructure is provided.

A variety of electronic circuit integrations such as an invertor, alogic element, a memory, a display, a backplane, RF, AC, DC, etc. basedon the CMOS-type structure may be formed into a large area.

Now, the present invention will be described in more detail withreference to the following examples. These examples are provided onlyfor illustration of the present invention and should not be construed aslimiting the scope and spirit of the present invention.

Example 1

Mo was deposited to a thickness of 20 nm on a Si substrate throughthermal CVD and then vaporized Se was diffused into the Mo film using aSe powder and MoSe₂ powder as raw materials according to CVD.Subsequently, the Mo film into which the vaporized Se and MoSe₂ werediffused was post-heated at 1200° C. for six hours, thereby obtaining aMoSe₂ film.

Experimental Example 1

On a MoSe₂ film according to Example 1, a Ti/Au electrode was formed asa source-drain, and a transistor film having a SiO₂ nonconductor and aSi gate structure was manufactured. Using a semiconductor analyzer(KEITHLEY 4200-SCS) as a current-voltage measurement device, electricalproperties of the transistor were evaluated.

FIG. 3 illustrates transfer curves of the transistor and FIG. 4illustrates output curves.

Device mobility was 60 to 100 cm²/vsec and characteristics of NMOS wereexhibited.

As described above, a film of a chalcogen compound represented by MX₂,wherein M is a transition metal element or a Group V element and X is achalcogen element, may be formed into a two-dimensional large-area athigh growth speed through a two-dimensional large-area growth method fora chalcogen compound according to the present invention and may exhibithigh flexibility and mobility, thereby being usefully used as anext-generation thin film semiconductor material.

Although the preferred embodiments of the present invention have beendisclosed for illustrative purposes, those skilled in the art willappreciate that various modifications, additions and substitutions arepossible, without departing from the scope and spirit of the inventionas disclosed in the accompanying claims.

DESCRIPTION OF SYMBOLS

-   -   1: NMOS    -   2: PMOS    -   3: substrate    -   100: CMOS-type structure    -   10: single-crystalline    -   20: poly-crystalline    -   30: noncrystalline    -   40: substrate    -   50: deposition material    -   60: laser beam

What is claimed is:
 1. A two-dimensional large-area growth method for achalcogen compound, the method comprising: forming a film of atransition metal element or a Group V, or Group VI element by depositingthe transition metal element or the Group V, or Group VI element on asubstrate; diffusing the chalcogen element, the chalcogen precursorcompound or the chalcogen compound represented by M′X′_(2+δ) into thefilm of the transition metal element or the Group V, or Group VI elementby contacting through vaporization at least one selected from the groupconsisting of a chalcogen element, a chalcogen precursor compound and achalcogen compound represented by M′X′_(2+δ) and combinations thereofwith the film of the transition metal element or the Group V, or GroupVI element, wherein M′ is a transition metal element or a Group V, orGroup VI element, X′ is a chalcogen element, and 0≦δ≦0.5; and forming afilm of the chalcogen compound represented by MX₂ by post-heating thefilm of the transition metal element or the Group V, or Group VI elementincluding the resultant diffused chalcogen element, chalcogen precursorcompound or chalcogen compound represented by M′X′_(2+δ), wherein M is atransition metal element or a Group V, or Group VI element and X is achalcogen element, wherein, in the film of the transition metal elementor the Group V, or Group VI element comprising the diffused chalcogenelement, precursor compound or chalcogen compound represented byM′X′_(2+δ), an atom ratio of the chalcogen element to the transitionmetal element or the Group V element is greater than
 2. 2. A method ofmanufacturing a CMOS-type structure, the method comprising: forming apatterned film of a first transition metal element or a first Group Velement on a substrate by patterning and depositing a first n-typetransition metal element or the first Group V, or Group VI element onthe substrate; forming a patterned film of a second transition metalelement or a second Group V, or Group VI element on a substrate bypattering and depositing a second p-type transition metal element or thesecond Group V element on the substrate; diffusing the chalcogenelement, the chalcogen precursor compound or the chalcogen compoundrepresented by M′X′_(2+δ) into the patterned film of the firsttransition metal element or the first Group V element and the patternedfilm of the second transition metal element or the second Group Velement by contacting through vaporization at least one selected fromthe group consisting of a chalcogen element, a chalcogen precursorcompound and a chalcogen compound represented by M′X′_(2+δ) andcombinations thereof with the patterned film of the first transitionmetal element or the first Group V element and the patterned film of thesecond transition metal element or the second Group V element, whereinM′ is a transition metal element or a Group V element, X′ is a chalcogenelement, and 0≦δ≦0.5; and obtaining a complementary metal oxidesemiconductor (CMOS)-type structure comprising an N channel metal oxidesemiconductor (NMOS) and a P channel metal oxide semiconductor (PMOS) byforming a chalcogen compound represented by MX₂ through post-heating ofthe patterned film comprising the diffused chalcogen element chalcogenprecursor compound or chalcogen compound represented by M′X′_(2+δ) andthus by forming a patterned film of the chalcogen compound representedby MX₂, wherein M is a transition metal element or a Group V element andX is a chalcogen element.
 3. The method according to claim 2, whereinthe vaporized chalcogen element, chalcogen precursor compound, orchalcogen compound represented by M′X′_(2+δ) vaporized into thepatterned film through a physical or chemical vapor-phase synthesismethod is diffused using at least one raw material selected from thechalcogen element, the chalcogen precursor or the chalcogen compoundrepresented by M′X′_(2+δ) and combinations thereof.
 4. The methodaccording to claim 2, wherein the vaporized chalcogen element, chalcogenprecursor compound or chalcogen compound represented by M′X′_(2+δ)diffused into the patterned films is migrated by a carrier gas anddiffused into the film.
 5. The method according to claim 2, wherein, inthe patterned film comprising the diffused chalcogen element, precursorcompound or chalcogen compound represented by M′X′_(2+δ), an atom ratioof the chalcogen element to a total of the transition metal element orthe Group V element is greater than
 2. 6. The method according to claim2, further comprising recrystallizing the chalcogen compound representedby MX₂ by annealing the CMOS-type structure obtained through thepost-heating.